AU716406B2

AU716406B2 - Use of 1,2,3-thiadiazolecarboxylic (thio)esters for controlling pests and novel 1,2,3-thiadiazolecarboxylic (thio)esters

Info

Publication number: AU716406B2
Application number: AU10315/97A
Authority: AU
Inventors: Bernd Alig; Gerd Hanssler; Michael Londershausen; Klaus Stenzel; Andreas Turberg
Original assignee: Bayer AG
Current assignee: Bayer AG
Priority date: 1995-12-07
Filing date: 1996-11-25
Publication date: 2000-02-24
Anticipated expiration: 2016-11-25
Also published as: ATE206280T1; CN1208324A; EP0865240A1; CN1112849C; WO1997020465A1; AU1031597A; EP0865240B1; CA2239710A1; DE19545638A1; KR100472001B1; DE59607847D1; BR9611700A; KR19990071694A; JP2000501102A

Abstract

The invention relates to the use of partially known 1,2,3-thiadiazole carboxylic acid (thio)esters of formula (I), in which R<1> is hydrogen, optionally substituted alkyl or optionally substituted aryl; R<2> is optionally substituted alkyl, optionally substituted cycloalkyl, optionally substituted cycloalkenyl or optionally substituted aryl; and Q is oxygen or sulphur, and the use of acid addition salts and metal salt complexes of said esters to protect plants well from attack by undesirable micro-organisms and to control animal pests. Particular 1,2,3-thiadiazole carboxylic acid (thio)esters of formula (I) are novel.

Description

USE OF t, 2 ,3-TIIIDIAZOILCARBOXYUC (FHI)ESER FOR CONTROLLIN PESM AND NOVEL lZ,3-THKADIAZOLECARtBOXYUC

(FIIO)ESTERS.

The present invenltionl relates to the use of known and novel l2,3thiadiazolcCafboxyliC- (thio)esters for controlling u nwanted micro-organisms and ainimal Pests.

Certan l,23-thiadiazolcCarbOxYlic acid derivatives are already known (cf. DE-A- 2728 1523). However. only herbicidal and plant-growth-regulatiflg properties of these compounds have hitherto been described.

It has now been found that 1 ,2,3tidaZlaZIXYC(hoesrsftefrua N

S

inwhchth rdial R' adQhv h9enig e oteo RI Q N CH 0 S:1 1 -2-

-C

6

H

5 0 CH 3 CH 3 "-04CH 3

-CH

3 00

-CH

3 0 CH 3 3CH 3 -3-

-CH

3 cI -CH 3 4. 4 4

S

S*

S

4O S 4 *544

S

*SS.

*4*t*4

S

5 4 4 4*S@

S

S S *5

S

-CH

3

-CH

3

H

3

C

C H 3 I_ CH 3

-CH

3

-CH

3

-CH

3

CH

3 0 N -a Ci

-CH

3 RlQ

R

2

-CH:

3 0

CH

3 CH 3

-CH

3

CA

pp p.

pp p p p*p p PP pp p *p p p p pp p p p.

p

-CH

3

-CH

3

-CH-

3 ac Cl aCI Al cI aOCH3

-CH

3

-CH

3 01

-CH

3 9* :s Sb U ft U ft .5 ft U.

*Ua.

ft a an.

a a ft a a 4* 9

U

-CH

3 cI CF 3

F

I

F

F* CF 3

F

cI OC F 3

-CH

3

-CR

3

-CH

3

NO

2 RlQ R 2

-CH

3 0

CF

3

-CH

3 0 10CH 3

CH

3 0 OH 3

H

3 15 i

-CH

3 0

H

3 0 0

-CH

3 0 B r OC3 -CH 0 C H 3 0HB CH 3 -7-

-CH-

3 0 N "CF 3

CH

3 0C /7 CH 3 S: -C H

I

H99 0 CF3 3 1 7 0

CH

3

-CH-

3 0 H1-jG /CH 3

-CRF

3 0

H

3 C C H 3 jw %rCH 3

H

3 C

CH

3

-CH

3

C.

eq C a

C

.C..Cq

C

C. C C

C

C. CC

C

SCS.

C.

S C

C..

CC

SC

C C

C

CC

eq C C* CC F a eq

C

-CH

3

H

3 C PH 3

C

2

H

-CR

3 0 'O>CH 2

F

CH2F

-CH

3

-CH

3 o CF 3

-CH

3 -9- RlQ

R

2

-CH

3 0 t 2

HA

-CR

3 0 -O

CCH

-CH

3 0 3 0* a-CH 3 0 0CF 3 -CH3 0CH 3 -CH 0 0"4 Cl- 3

CH

3

-CR

3 0N 0~l'

-CH-

3 0

CH

3

CH

3

-CH

3 0 F

F

*.-CH

3 0H3c C -CH 3 0

*S-CH

3 0 O c 3 fC.

OINCI

-11 I-

-CH

3

-CH

3 lo.

0 94 9 20

-CH

3 CH(CH 3) 2

CH(CH)

2 0 cI

CI

-CH

3

-CH

3

-CH

3

C(CH

3 3

-CH

3 0 H -12-

-CH

3 CF 3

-CH

3 9.

*9 9 9 999 999*99 9 9. .9 9 9 9 9 9 9 *9*t*9 9 9* 9* 9**9 9 9 09 .9 999* 9 9 9999 999999 9 99 *9 9 999.

9. 9 9* .9 9

-CH-

3

-CH

3

CH

3

-CH

3

CF

3

CAH

CH

3 -Cl- 3

-CH

3 0,CAH 0 13

RQ

-CH

3 0

CH

3

~OCH,

CH

3

-GE

3 0 1 4 0 0 *CH 0-F CH 10 Atet

CHCI

3 -14the same direction of action.

The 1 ,2,3-thiadiazolecarboxylic (thio)esters of the formula

N-

I/

Q, 2 10 in which the radicals R? and Q have the meanings set forth above are novel compounds.

S

S S

S*

9.

S

*55S

S

.5 S a

S

S5 S S S S 55 S S 15 The I ,2,3-thiadiazo lecarboxylic (thio)esters of the formula can be prepared by reacting 1 ,2,3-thiadiazolecarboxylic acid derivatives of the formula OX~ 11

"ONO

.0 6: *6 S 00.0.

66* 0.

ON:

in Which 15 -Rl is as defined above and x represents hagen with (thio)inlcobols of the frormula H Q-R 2 in which Q and e 2 amu each as defined above, if appropriate in the presence of an acid binder and if appropriate in the presence of a diluent.

-16- The 1,2,3-thiadiazolecarboxylic (thio)esters of the formula usable according to the invention may, if desired, be obtained as mixtures of different possible isomeric formns, in particular in the form. of stereoisomers. The invention re-lates both to the pure isomers and to any mixtures thereof.

If 4-methyl-i Z,3-thiadiazole carbonyl chloride and 4 -trifluoromethylbenzyl alcohol are used as starting materials, the course of the process according to the invention can be illustrated by. the following equation: 9e 9 4 4 9 4*9949 9 9. S.

4 9 9 999.

9 9 49999 0 *9 99 9.

9.

9.9.

4 .9.9 *9*99* 0

S.

9 0 44 4 99 9 4* 4 9~ 9 CH 3

N

NNS

0 IBase 4-HC1

F

3

OC

The formula (11) provides a general definition of the 1 ,2,3-thiadiazolecarboxylic acid derivatives required as starting materials for carrying out the process according to the invention. In this formula R 1 has those meanings which have already been indicated in connection with the description of the compounds of the formula according to the invention for X preferably represents chlorine.

The 1,2,3-thiadiazolecarboxylic acid derivatives of the formula (11) are known or can be prepared by processes known per se (cf. DE-A-2 728 523 or 1. Heterocyclic Chem.

301).

17 The formula (Ill) provides a general definition of the (thio)alcohols furthermore required as starting materials for carrying out the process according to the invention. In this formula (111), Q and W 2 each have those meanings which have already been indicated in connection with the description of compounds of the formnula according to the invention for Q andR.

The (thio)alcohols of the formula (111) are known reagents of organic chemistry.

Suitable acid binders for carrying out the process according to the invention -ame all customary inorganic and organic bases. Preference is given to using alkaline ea'rthmetal 00644: 10 or alkali metal hydrides, hydroxides, amnides, alkoxides, acetates, carbonates or bicarbonates, such as, for example, sodium hydride, sodium amide, sodium methoxide, sodium ethoxide, potassium tert-butoxide, sodium hydroxide, potassium hydroxide, potassium acetate, calcium acetate, sodium carbonate, potassium carbonate, potassium bicarbonate, sodium bicarbonate, furthermore basic ammnonium compounds, such as 15 amnmonium hydroxide, ammonium acetate or armmonium carbonate, and tertiary amines, such as trim ethylamine, triethylamine, tributylainine, NN-dimethylaniline, N,N4d imethyl-benzylamine, pyridine, N-methylpiperidine,. N-methylmorpholine, NN- *se* dimcthylarninopyridine, diazabicyclooctane (DABCQ), diazabicyclononcne (DN or diazabicycloundecene (DBU).

Suitable diluents for carrying out the process according to the invention are all customary inert organic solvents. Preference is given to using aliphatic, alicyclic or aromatic hydrocarbons, such as, for example, petroleum ether, hexanc, heptane, cyclohexane, methylcyclohexane, benzene, toluene, xylene or decalin; halogenated hydrocarbons, such as, for example, chlorobenzene, dichlorobenzene, dichioromethane, chloroform, carbon tetrachloride, dichioroethane or trichioroethane; ethers, such as diethyl ether, diisopropyl ether, methyl t-butyl ether, methyl t-amyl ether, dioxane, tetrahydrofiiran, I ,2-dirnethoxyethane, I ,2-diethoxyethane or anisole; ketones, such as acetone, butanone, methyl isobutyl ketone or cyclohexanone; nitriles, such as R -aeontie propionitrile, n- or i-butyronitrile or benzonitrile; amides, such as N,N- ~i\~nth Iformamide, NN-dimnethylacetamide, N-methylformanilide, N-methylpyrrolidone 18or hexamethylphosphoric triamide; esters such as methyl acetate or ethyl acetate; sulphoxides, such as dimethyl sulphoxide; sulphones, such as sulpholane.

When carrying out the process according to the invention, the reaction temperatures can be varied within a relatively wide range. In general, the reaction is carried out at temperatures between -20*C and +180"C, preferably at temperatures between 20"C and 130°C.

The process according to the invention is usually carried out under atmospheric pressure. However, it is also possible to operate under elevated or reduced pressure.

When carrying out the process according to the invention, generally 0.5 to 10 mol, preferably 0.8 to 3 mol, of (thio)alcohol of the formula (III) are employed per mole of the 1,2,3-thiadiazolecarboxylic acid derivative of the formula The reaction is carried out and worked up by known methods (cf. Preparation Examples).

The active compounds usable according to the invention have a strong resistanceinducing activity in plants. They are therefore suitable for generating resistance in plants against attack by unwanted microorganisms.

S Resistance-inducing compounds in the present context are substances which are capable of stimulating the defence system of plants in such a way that the treated plants, when subsequently inoculated with unwanted microorganisms, are largely resistant against these microorganisms.

In the present case, unwanted microorganisms are phytopathogenic fungi, bacteria and viruses. Thus, the compounds according to the invention can be employed to generate resistance in plants against attack by the abovenentioned harmful organisms for a certain period after the treatment. The period for which resistance is generated generally extends over 1 to 10 days, preferably 1 to 7 days, after the treatment of the plants with /th4ctive compounds.

19- In addition to the resistance-inducing activity, the active compounds usable according to the invention also have strong microbicidal activity, and they are also employed in practice for the direct control of unwanted microorganisms. The active compounds are suitable for use as crop protection agents, in particular as fungicides.

In crop protection, unwanted microorganisms include fungi from the classes of the Plasmodiophoromycetes, Oomycetes, Chytridiomycetes, Zygomycetes, Ascomycetes, Basidiomycetes, Deuteromycetes.

1 Bactericides are employed in crop protection for controlling Pseudomonadaceae, Rhizobiaceae, Enterobacteriaceae, Coryniebacteriaceae and Streptomycetaceae.

Some pathogens causing fungal and bacterial diseases which come under the generic *.Ogg: names listed above are mentioned as examples, but not by way of limitation: 15 Xanthomonas species, such as, for example, Xanthomonas campestris pv. oryzae; Pseudomonas species, such as, for example, Pseudomonas syringae pv. lachrymans; Erwinia-species, such as, for example, Erwinia amylovora; Pythium species, such as, for example, Pythium ultimum; Phytophthora species, such as, for example, Phytophthora infestans; 20 Pseudoperonospora species, such as, for example, Pseudoperonospora hurnuli or Pseudoperonospora cubensis; Plasmopara species, such as, for example, Plasmopara viticola; Bremia species, such as, for example, Bremia lactucae, Peronospora species, such as, for example, Peronospora pisi or P. brassicae; Erysiphe species, such as, for example, Erysiphe graminis; Sphaerotheca species, such as, for example, Sphaerotheca fuliginca; Podosphaera species, such as, for example, Podosphaera leucotricha; Venturia species, such as, for example, Venturia inacqualis; ,..,Pyrenophora species, such as, for example, Pyrenophora teres or P. graminea R nidia form: Drechslera, syn: Helminthosporiurn); Cochliobolus species, such as, for example, Cochliobolus sativus (conidia form: Drechslera, syn: Helminthosporium); Uromyces species, such as, for example, Uromyces appendiculatus; Puccinia species, such as, for example, Puccima recondita; Sclerotinia species, such as, for example, Sclerotinia sclerotiorum; Tilletia species, such as, for example, Tilletia caries; Ustilago species, such as, for example, Ustilago nuda or Ustilago avenae; Pellicularia species, such as, for example, Pellicularia sasakii; Pyricularia species, such as, for example, Pyricularia oryzae; S 10 Fusarium species, such as, for example, Fusarium culmorum; Botrytis-species, such as, for example, Botrytis cinerea; Septoria species, such as, for example, Septoria nodorum; 9 Leptosphaeria species, such as, for example, Leptosphaeria nodorum; Ccrcospora species, such as, for example, Cercospora canescens; 15 Alternaria species, such as, for example, Altemaria brassicae; and Pseudocercosporella species, such as, for example, Pseudoccrcosporella herpotrichoides.

The fact that the active compounds are well tolerated by plants at the concentrations required for controlling plant diseases permits the treatment of aerial parts of plants, of 20 propagation stock and seeds, and of the soil.

The active compounds usable according to the invention can be employed particilarly successfully for controlling rice diseases, such as Pyricularia species, or diseases in viticulture and fruit and vegetable growing, such as, for example, Uncinula species, and they can also be employed very successfully against cereal diseases such as powdery mildew.

Depending on their particular physical and/or chemical properties, the active compounds can be converted to the customary formulations, such as solutions, emulsions, %Rq suspensions, powders, foams, pastes, granules, aerosols and microencapsulations in polymeric substances and in coating compositions for seeds, and ULV cool and warm 1//fo2iine formulations.

-21- These formulations are produced in a known manner, for example by mixing the active compounds with extenders, that is liquid solvents, liquefied gases under pressure, and/or solid carriers, optionally with the use of surfactants, that is emulsifiers and/or dispersants, and/or foam formers. If the extender used is water, it is possible to use for example organic solvents as auxiliary solvents. Essentially, the following are suitable as liquid solvents: aromatics such as xylene, toluene or alkylnaphthalenes, chlorinated aromatics or chlorinated aliphatic hydrocarbons such as chlorobenzenes, chloroethylenes or methylene chloride, aliphatic hydrocarbons such as cyclohexane or paraffins, for example petroleum fractions, alcohols such as butanol or glycol and their ethers and 10 esters, ketones such as acetone, methyl ethyl ketone, methyl isobutyl ketone or cyclohexanone, strongly polar solvents such as dimethylformamide or dimethyl sulphoxide, or else water. Liquefied gaseous extenders or carriers are to be understood as meaning liquids which are gaseous at standard temperature and under atmospheric *9*999 S' pressure, for example aerosol propellants such as halogenated hydrocarbons, or else butane, propane, nitrogen and carbon dioxide. Suitable solid carriers are: for example ground natural minerals such as kaolins, clays, talc, chalk, quartz, attapulgite, e montmorillonite or diatomaceous earth, and ground synthetic minerals such as highly S disperse silica, alumina and silicates. Suitable solid carriers for granules are: for example crushed and fractionated natural rocks such as calcite, marble, pumice, sepiolite 20 and dolomite, or else synthetic granules of inorganic and organic meals, and granules of organic material such as sawdust, coconut shells, maize cobs and tobacco stalks.

Suitable emulsifiers and/or foam formers are: for example nonionic and anionic emulsifiers, such as polyoxyethylene fatty acid esters, polyoxyethylene fatty alcohol ethers, for example alkylaryl polyglycol ethers, alkylsulphonates, alkyl sulphates, arylsulphonates, or else protein hydrolysates. Suitable dispersants are: for example lignin-sulphite waste liquors and methylcellulose.

-22- Tackifiers such as carboxymethylcellulose and natural and synthetic polymers in the form of powders, granules or latices, such as gum arabic, polyvinyl alcohol and polyvinyl acetate, or else natural phospholipids such as cephalins and lecithins and synthetic phospholipids can be used in the formulations. Other additives can be mineral and vegetable oils.

It is possible to use colorants such as inorganic pigments, for example iron oxide, titanium oxide and Prussian Blue, and organic dyestuffs such as alizarin dyestuffs, azo dyestuffs and metal phthalocyanine dyestuffs, and trace nutrients such as salts of iron, manganese, boron, copper, cobalt, molybdenum and zinc.

e..

The formulations generally comprise between 0.1 and 95 per cent by weight of active compound, preferably between 0.5 and -9 The active compounds usable according to the invention can be used as such or in their formulations also mixed with known fungicides, bactericides, acaricides, nematicides or insecticides in order thus, for example, to widen the spectrum of action or to prevent development of resistance. In many cases, synergistic effects are achieved, i.e. the activity of the mixture exceeds the activity of the individual components.

:o Examples of suitable co-components in mixtures are the following compounds: -23 Fungicides: 2-aminobutane; 2 -anilino- 4 -rnethyI-6-cyclopropyI-pyrimidine; 2 ibrorno- 2 -met'ayl-4'-tri D uoromethoxy-4'trifluoromethy. I 1,3-thiazole-5 -carboxanilfide; 2,6-dichloro-N-(4-trifluoronethylbnzy)benzamnide; (E)-2-rnethoxyimino-N-rnethyl-2-(2phenoxyphenyl)acetamide, 8-hydroxyquinoline siulphate; methyl-(E)-2- 2 -[6-(2-cyanophenoxy)pyrim idin-4-yloxy]-phenyl )-3-methoxyacrylate; rnethyl-(E)-methoximi no [alpha-(o-talyloxy)-o-tolyl] acetate; 2-phenyiphenol (OPP), aldimorph, ampropylfos, anilazine, azacoriazole, 10benalaxyl, benodanil, benornyl, binapacryl, biphenyl, bitertanol, blasticidin-S, -bromuconazole, bupirirnate, buthiobate, 9* calcium polysuiphide, captafol, captan, carbendazim, carboxin, quinomethionate, chloroneb, chioropicriri, chiorothalonil, chiozolinate, cufraneb, cynioxanil, cyproconazole, cyprofuram, dichiorophen, diclobutrazole, diclofluanid, diclomezine, dicloran, diethofencarb, 15difenoconazole, diniethirimol, dimetbornorph, diniconazole, diriocap, diphenylamine, dipyrithione, ditalimfos, dithianon, dodine, drazoxolon, edifenphos, epoxiconazole, ethirirnol, etridiazole, .9 feriarimol, -fenbuconazole, fenfurani, fenitropaa, fenpiclonil, fenpropid in, fenpropimorph, acetate, fentin hydroxide, ferbarn, ferimzone, fluazinam, fludioxonil, fluoromide, fluquinconazole, flusilazole, flusulfarnide, flutolanil,flutriafol, folpet, fosetyl-aluminium, fthalide, fuberidazole, furalaxyl, furmnecyclox, guazatine, hexachlorobenzene, hexaconazole, hyniexazole, imazalil, irnibenconazole, irninoctadine, iprobenfos (IBP), iprodione, isoprothiolane, kasugamycin, copper preparations, such as: coppr hydroxide, copper naphthenate, copper oxychioride, copper sulphate, copper oxide, oxine-copper and Bordeaux mixture, mnancoppgr, mancozeb, maneb, mepanipyrini, mepronil, jnetalaxyl, metconazole, methasulfocarb, methfuroxam, metiram, metsulfovax, niyclobutanil, '~$~~'YTickel dimethyldithiocarbarnate, nitrothal-isopropyl, nuarimol, 7- A fA'race, oxadixyl, oxamocarb, oxycarboxin, 24 pefurazoate, penconazole, pencycuron, phosdiphen, pimnaricin, piperalin. polyoxin, probenazole, prochloraz, procymnidone, propamocarb, propiconazole, propineb, pyrazophos, pyrifenox, pyrimethanil, pyroquilon, quintozene

(PCNB),

sulphur and sulphur preparations, tebuconazole, tecloftalain, tecnazene, tetraconazole, thiabendazole, thicyofen, thiophinate-melthyI. thiramn, toiclofos-methyl, tolyifluanid, triadimefon, triadimenol, triazoxide, tri chiamide, tricyclazole, tridemnorph, triflumnizole, tniforine, triticonazole, validamycin A, vinclozolin, 10 zineb, ziramn.

Bactericides: brornopol, dichioropheri, nitrapyrill, nickel dim ethyldithi ocarbamlate, kasuganycira, octhilinone, furancarboxylic acid, oxytetracyclin, probenazole, streptomnycin, tecloftalamn, 15 copper sulphate and other copper preparations.

CC InecticideslAcaicidesNematicides: abamnectin, acephate, acrinathrifl, alanycarb, aldicarb, alpharnethrin, amitraz, avermectin, AZ 60541, azadirachtin, azinphos A, azinphos M, azocyclotin, thuringienSiS, 4bromo-2-(4-chIo[0phenfl-i -(ethoxymethyD)-5 -(trifi uoromrethyl)- I l-pyrrole- 3 -carbonitrile, bendiocarb, benfuracarb, bensultap, betacyfluthrifl, bifenthrin, BPMC, brofenprox, bromnophos A, bufencarb, buprofezin, butocarboxim, butylpyridaben,I cadusafos, carbaryl, carbofurari, carbopheriothion, carbosulfan, cartap, chloethocarb, chiorethoxyfoS, chiorfenviriphos, chlorfluazurofl, chiormephos, N-[(6-chloro-3-pyrid inyl)rnethyl-N'-cyano-Nmethyl-ethanimidamide, chiorpyrifos, chiorpyrifos M, cisrcsmethrin, clocythrin, clofentezifle, cyanophos, cycloprothrin, cyfluthrin, cyhalothrin, cyhexatin, cyperiethriri, cyromnazifle, deltarnethrifl, demeton M, demneton S, derneton S-methyl, diafenthiurori, diaiinon, Fw- Fidichlofeflthiofl, dichlorvos, dicliphos, dicrotophos, diethion, diflubenzurofl, dimnethoate, 25 dinethytvinphos, dioxathion, disulfoton, edifenphos, emamnectin, esfenvalerate, ethiofencarb, ethion, ethofenprox, ethoprophos, etrimphos, fenamiphos, fenazaquin, fenbutatin oxide, fenitrothion, fenobucarb, fenothiocarb, fenoxycarb, fenpropathrin, fenpyrad, fenpyroximate, fenthion, fenvalerate, fipronil, fluazinam, fluazuron, flucycloxuron, flucythrinate, flufenoxuron, flufenprox, fluvalinate, fonophos, forrnothion, fosthiazate, ftibfenprox, furathiocarb, HCH, heptenophos, hexaflumnuron, hexythiazox, imidacloprid, iprobenfos, isazophos, isofenphos, isoprocarb, isoxatlion, iverrnectin, Iainbda-cyhalothrin, lufenuron, malathion, inecarbam, mervinphos, mesulfenphos, inetaldehyde, methacrifos mrthaznidophos, methidathion, rnethiocarb, methomyl, metolcarb, milbemectin, monocrotophos, moxidectin, naled, NC 184, nitenpyrarn 15 omethoate, oxamyl, oxydemethon M, oxydeprofos, parathion parathion M, permethrin, phenthoate, phorate, phosalone, phosrnet :phosphamidon, phoxini, pirimicarb, pirirniphos M, pirimiphos A, profenophos, promecarb, propaphos, propoxur, prothiofo's, prothiophos, prothoate, pyrnetrozin, pyrachiophos, pyridaphenthion, pyresrnethrin, pyrethrum, pyridaben, pyrimidifen. pyriquinaiphos, salithion, sebufos, silafluofen, sulfotep, sulprofos, tebufenozide, tebufenpyrad, tebupirirnphos, teflubenzuron, tefluthrin, temephos, terbamn, terbufos, tetrachlorvinphos, thiafenox, thiodicarb, thiofanox, thiornethon, thionazin, tralomethrin, triarathen, triazophos, triazuron, trichlorfon, trifi umuron, trimethacarb, yarnidothion, XMC, xylylcarb, zetamethrin.

q 't~s also possible to admix other known active compounds, such as herbicides, or e-ilizers and growth regulators.

0 -26- The active compounds usable according to the invention can be used as such or in the form of their commercial formulations or the use forms prepared therefrom, such as ready-to-use solutions, suspensions, wettable powders, pastes, soluble powders, dusts and granules. They are used in the customary manner, for example by wetting, spraying, atomizing, broadcasting, foaming, brushing-on and the like. It is further possible to apply the active compounds by the ultra-low volume method or to inject the preparation of active compound, or the active compound itself, into the soil. The seeds of the plants can also be treated, if appropriate.

10 In the treatment of parts of plants, the active compound concentrations in the use forms can be varied within a substantial range. They are, in general, between I and 0.0001% by weight, preferably between 0.5 and 0.001% by weight.

In the treatment of seed, amounts of active compound of from 0.001 to 50 g, preferably 0.01 to 10 g, are generally required per kilogram of seeds.

*1* In the treatment of the soil, active compound concentrations of from 0.00001 to 0.1% by weight, preferably from 0.0001 to 0.02% by weight, are required at the site of action.

20 The active compounds according to the invention are also active against plant, hygiene and stored-product pests, and also, in the veterinary medicine sector, against animal parasites (ectoparasites), such as ixodid ticks, argasid ticks, scab mites, trombiculid mites, flies (stinging and sucking), parasitic fly larvae, lice, hair lice, bird lice and fleas.

These parasites include: From the order of the Anoplurida, for example, Haematopinus spp., Linognathus spp., Pediculus spp., Phtirus spp., Solenopotes spp.

From the order of the Mallophagida and the sub-orders Amblycerina and Ischnocerina, example, Trimenopon spp., Menopon spp., Trinoton spp., Bovicola spp., WtMeckiella spp., Lepikentron spp., Damalina spp., Trichodectes spp., Felicola spp.

7w^ 27 From the order Diptera and the sub-orders Nematocerina and Brachycerinaj or example, Aedes spp., Anopheles spp., Gulex spp., Simulium spp., Eusimulium spp., Phlebotomus spp;, Lutzomyia spp., Culicoides spp., Chrysops spp., Hybornitra spp., Atylotus spp., Tabanusspp., Haematopota, spp., Philipomyia spp., Braula spp., Musca spp., Hydrotaea Stomoxys spp., H-aematobia spp., Morellia spp., Fannia spp., Glossina spp.., Calliphora spp., Lucilia spp., Chrysomyia spp., Wohlfahrtia spp., Sarcophaga spp., Oestrus spp., Hypoderma spp., Gasterophilus spp., Hippobosca spp., Lipoptena spp. and Melophagus spp.

From the order of the Siphonapterida, for example, Pulex spp., Ctenocephalides spp., Xenopsyjla spp. and Ceratophyllus spp.

'From the order of the 1-eteropterida, for example, Cirnex spp., Triatoma spp., Rhodnius spp. and Panstrongylus; spp.

From the order of the Blattarida, for example, Blatta orieritalis, Periplaneta americana, Blattela. germanica and Supella spp.

From the sub-class of the Acaria (Acarida) and the orders of the Meta- and Mesostigrnata, for example Argas spp.. Ornithodorus spp., Otobius spp., Ixodes spp., Amnblyornma spp., Boophilus spp.,* Dermacentor spp., J-aemophysalis spp., Hyalomma 20 Rhipicephalus spp., Derrnanyssus spp., Raillietia, spp., Pneumonyssus spp., Sternostoma spp. and Varroa spp.

From the order of the Actinedida (Prostigmata) and Acaridida (Astigmata), for example Acarapis spp., Cheyletiella spp., Ornithocheyletia spp., Myobia spp., Psorergates spp., Demnodex spp., Trombicula spp., Listrophorus; spP., Acarus spp., Tyrophagus spp., spp., Hypodectes spp., Pterolichus spp., Psoroptes spp., Chorioptes spp., Octodectes spp., Sarcoptes spp., Notoedres spp., Knemidocoptes spp., Cytodites spp. and -Laminosioptes spp.

6-V q eyhave outstanding activity for example against Musca domnestica and Lucilia C 1 na larvae.

O$V

7 -28- The active compounds usable according to the invention are also suitable for controlling arthropods which attack agricultural livestock, such as, for example, cattle, sheep, goats, Shorses, pigs, donkeys, camels, buffalo, rabbits, chickens, turkeys, ducks, geese, honey Sbees, other domestic animals, such as, for example, dogs, cats, cage birds, aquarium fish, and so-called experimental animals such as, for example, hamsters, guinea-pigs, rats and mice. By controlling these arthropods, it is intended to reduce mortality and decreased performance (in meat, milk, wool, hides, eggs, honey and the like), so that more economical and simpler animal keeping is made possible by using the active compounds according to the invention.

In the veterinary sector, the active compounds usable according to the invention are used in a known manner by enteral administration, for example in the form of tablets, capsules, drinks, drenches, granules, pastes, boluses, the feed-through method, 1suppositories, by parenteral administration, such as, for example, by means of injections (intramuscular, subcutaneous, intravenous, intraperitoneal and the like), implants, by nasal application, by dermal administration, for example in the form of dipping or bathing, spraying, pouring-on and spotting-on, washing, dusting, and with the aid of shaped articles which comprise active compound, such as collars, ear tags, tail marks, 20 limb bands, halters, marking devices and the like.

C

When administered to livestock, poultry, domestic animals and the like, the active compounds can -be used as formulations (for example powders, emulsions, flowables).

which comprise the active compounds in an amount of 1 to 80% by weight, either directly or after dilution by a factor of 100 to 10,000, or they may be used in the form of a chemical bath.

The preparation and the use of the active compounds usable according to the invention is illustrated by the examples below.

29 Pre Ma~i&n -Ex ames Fxamnie 1:

N-

N I

S

9 9 6

V

a. *e 6 9 6 a 996ae* .9 V 9 9* V 9 9 a *99V** 9 a *9 9

V.

10 A solution of 6.5 g (39.6 mmol) of 4-t-butylbenzyl alcohol and 15 ml of trniethylarnine in 100 ml of toluene is admixed with 5.5 g (33.8 mmol) of 4-ethyl-1,2,3-thiadiazole- 5-carbon)'1 chloride and stirred at 100'C for 18 hours. Afler cooling, the reaction mixture is admixed with water. The organic phase is separated off, dried over magnesium sulphate and evaporated. The oil that remains is subjected to a Kugelrohr distillation. 6.7 g (68% of theory) of '4-t-butylbenzyl 4-inethyl1l,2,3-thiadiazoleC :5-carboxylate are obtained as an oil of boiling point 200*C at 0.1 mbar.

Example 2: 20

CH

3

N

S

0 A solution of 4 g (22.2 mmol) of 4-t-butylbenzeflethiol and 10 ml of triethylamine in ml of toluene is admixed with 3.5 g (21.5 mmol) of 4.rnethyl-1,2,3-thiadiazolechloride and stirred at 1 00'C for 18 hours. After cooling, the reaction mixture is admixed with water. The organic phase is separated off, dried over.

)T~(agnesium. sulphate and evaporated. The oil that remains is subjected to a Kugelrohr ~tillation. 4.0 g (61% of theory) of 4-t-butylbenzyl 4-methyl-1,2,3-thiadiazole" c§Lhiocarboxylate are obtained as a yellow oil of boiling point 210*C at 0.1 mbar.

Simiilarly to Examples I and 2, and according to the procedures in the description, the compounds listed in Table I below are obtained.

Rk Table 1: .0 0. 0.

.0* phys. data 15

S.

S S *5 S5S* 5 4

S

4.

4

S

e5** *4 S 4 20 5

-CH

3

-CH

3

CH

3 0H

CH

3

CH

3

CH

3 *)IH NMR 7,89-7,27 (9H); 5,31; 1,33 (9H) bp: 0.1mb 220 0

C

*)1H NMR 4,54 (2H1); 3,04 (2H1); 1,31 (9H) 6 -CH 3 bp: O.1mb 190 0

C

7 -CH 3 ")IH NMR 5,52 (211); 7,58- 7,21 (3H) -31 Table 1: (continuedl Ex.

No.

phys. data 1 1H

NMR

8 -CH 3

-CH

3 *9 99 9

S

999 9 999999 9 9. 99 99 9 9 9 999k 9 9 9 4999 9# 9* 9.

9.

.9.9 9 9 9 99.9 *99909 9 9 9 9 9.99 99 9 99 9 9* 9 10 -CH3 11 -cl- 3 12 -CR 3

H

3

C

S/ CH 3

H

3

C

aOCF 3 I H 3

CH

o CH 3 -Lc 5,33; 7,38-6,98 (9H) "1IH NMR 3,09 4,43 2,37 (6H); 6,88 2,26 (3H) bp: 0.1 mb I80 0 Cc bp:o, mb 190 0

C

bp: 01 mb 190 0

C

-CH3 'N /0

C'

O"iH NMR 4,76 5,96- 5,83 1,37 (3H) 32 Table 1: (continued) Ex.

No.

phys. data bp: o.i mb 14 -CH 3 200 0

C

CH

3 7-CH 3

-CH

3

C.

C

0 000 S C CCC..

C

0* SR 00 S

C

9@~R

C

SC.

0 0eO*

C.

*C

OC

'CRC

C C Re

CC

C

S

SC..

C

0 0e C 0 0O 0 CR C

C

0O

C

CH

3 0 I

N-C

2

HS

0 15 16 17

-CH

3

-CH-

3

-CH

3 Nl

CI

Nl

CI

*)IH NMR 4,74 1,34 (3H) *)IH NMR 5,38 7,49 (4H-) *)IH NMR 5,39 7,79- 7,47 (3H) H NMR 5,43 7,47- 7,29 (3H)

-CH

3 aOCH 3 bP: 0,1 b% 200 0

C

33 Dble 1: (continued) Ex.

No.

phys. data *IiF

-CH

3 7,10 (1 H)

-CH

3 ci CF 3 4 4 4 4* 4 4* .4 ')IH NMR 5,52; 7,72 (OH); 7,5 8 (2H) *)IH NMR 5,55 (2H) -CH3

CF

3

-CH-

3

CI

OCF 3 bp: o.1 mb 1901 0

C

-CH

3 ')IH NMR 5,48 (2H)

-CH-

3 N0 2 mp.: 101,C 34 Table 1: (continued) Ex.

No.

phys. data 26 -GCl 3 aCF3 H NMR 5,43 7,68- 7,46 (4H) 4.

4* 4 4 444 *4*4*4 4 .4 4* .4 4 *4 4 4 44 4 .4 44 4 27 -CH3 28 -CH 3 29 -CH 3 30 -CH3 aCH 3

/-\ZH

3 \o-0

CH

3

CH

3

H

3

C

-OCF

3 Br

OCF

3

CH

3

CH

3 bp: O. mb 17OVC bp: 0. ub 200 0

C

*)IH NMR 1,50; 5,50 OH1-); 4,12 7,32- 6,89 bp: o. mb 190 0

C

-cH- 3 32 bp: 0,1mb 206 0

C

bp: 02 nib 210 0

OC

bp:. 0.2 mb 200 0

C

Table 1: (continued) phys. data Ex.

No.

~1H

NMR

34 -C3 0

NCF

3 0 5,40 8,28- 7,21 (6H)

CH

9* a a a a a *5a* a a a a.

*5 a

S

a.

a a a a

CH

3 CH 3

OCF

3 bp: o02 _b 200 0

C

bp: 0.2 mb I

-C

3

H

7

-C

3

H

7

-CH

3

CH

3

CH

3 CH3 I l'

-C

6

H.

5 bp: 02 nb 190 0

C

bp: 0, nib OIH NMR 3,65; 2,57; 2,35 (6H-) bp: 0.1 nib 160 0

C

O"1H NMR 4,88 0,73 (6H)

I-CH

3 36 Table 1: (continued) Ex.

No.

phy3s. data 42 CH 3 HC CH 3 b w r CH 3

H

3 C

CH

3 bp: I.mb 210 0 cC .4 4 44 4 4 444*ee 4* 4 4444 4*4* 4 .4 40 4* .4 4 .4 4 4.4.

4 4*

S.

4 43 -CH 3 44 -CH3 45 -CH 3 46

-CH

3 HC CH.

C

2

H

5

CH

2

F

*1IH NMR 4,68 4,27 7,27-7,24 6,86-6,83 (2H) *)1H

NMR

4,51 3,98 4,6 (2H); 4,45 (2H) *)IH NMR 4,52 3,96 3,93 (2H) bp: 0.1 mb 200 0

OC

bp: 0.1 mb 180 0

C

47

-CH

3 0,,".,CF3 -37- Tabe 1: (continued) Ex.

No.

phys. data 48

-CH

3

N.

bp: 0.1 mb 180 0

C

49

-CH

3 9 .4 9* 9 4 4 .9 4.

4 9 9

-CH

3 -CH3 C H F2

COOCH

3 0CF 3

CH

3 -04CH 3

CH

3

N.N

0

N

O"1H NMR 4,48 3,74 3,50 (2H); 3,66 7;21- 6,64 1,14; 2,39 ")1H NMR 2H); 4,35 (2H); 3,89; 8,01 (2H); 6,94 (2H) *)IH NMR 4,51 3,78 4,59 (2H) O"IH NMR 4,72 4,34 (2H)

NMR

7,46 7,13 1,34 (9H) mp.: 11900 -CH3

-CH

3

-CH

3 -38- Table 1: (continuedi

EE.

No.

phys. data -CH3 a C.HO-tert.

nip.: 161 0

C

9* 9 9 9*99** 9* 6 9 9 9 9*9* 9*99..

9 .9 9* 9.

9* 99 999999 9 9 9 9 9**9 9* 6* 9 56 -CH 3 57 -CH 3

CH

3 C H 3 "I1H NMR 7,29-7,04 (MH) "iIli NMR 7,49-6,84C(3H) 58 '-CH 3

CHO

H 3 c...CH 3 mp.: 99-I 00,C mp 91 *C *)IH NMR 4,45; 4,95; 1,09 7,46 7,18 (2H)

-CH

3 -39- Table 1:_(continued) -Ex.

No.

phys. data 61 -CH 3 62 -CH 3 9 9 0 9 .9 9.

9 0 6 9 6 9 6 9 *9990 6 9999 99 99 9.

9999 9 999999 9 99 96 9 9 9 .9 9 99 99

H

3 C CH 3 0 C mp.: 56-57*C -)IH NMR, 2,36 3,02 (3H) mp.: 120-J21'C 63 -Cl- 3

-CH

3 CE 0 N 65 -CH3

-CH

3

CH(CH,)

2 0

CH(CH

3 2 mp.: 166-167*C *)IH NMR 2,90 5,02 (2H) *)IH NMR 2,93 4,02 4,68 (2H) *)IH NMR 2,87 4,17 4,49 (2H)

-CH-

3 Tbe 1: (continued) Ex.

No.

phys. data "IH

NMR

68 -CH 3 2,88 4,24 5,63-5,68 (2H) 9 9* 99 9 9 9 9 *9*9 9 9 9 *99.

9 9.

99*~ 99 9.

9* 9 *99* 99*999 9 9.

9 9 9 9 9**9 99 9 99 .9 69 -CH 3 70 -CH 3 cI C H 3 C(CH 3 3 C H 3

CI

C H 3 nip.: mp.: 55 0

C-

mp.: 44C

-CH

3

-CH

3

CF

3 IH NMR 2,94 3,14 4,57 (2H) *)IH NMR 1,71 2,96 (3 6,14 (11-H)

-CH

3 -41- Table 1: (continued) No.

phys. data 74 -Cl-I 0 /CF3 "1H

NMR

2,97 4,95 (1H) 9e

S.

S

b

S

9e

S.

.5

S

p

S

5 *5

S.

V

-CIA,

76 -CIA,

CH

3 CH3

N-CH

3 CH3 '"1H NMR 1,81 2,30 2,96 (3 H); 329 (2H) *)II NMR 2,98 4,19 5,40 (lIH) mp.: 38-40'C -CH3I

CH

3

-CH-

3 -I~y 0,C 2 H 0 *IH NMR 1,31 3,00 4,28 (2H); 4,86 (2H)

-CIA,

"II NMR 2,7 7 (3 H) -42 Table 1: (Continued phys. data Ex.

No.

inrojs mp.: iuo~ -CH3 0 mp.: I UO -CHr-CHi-

S.

4 4 0 0 444 9O*4*4 4 4 00 *e IS 4 0 .4.4 4 4 0e@*04

I

*4.4 0t .0 4.

-A

0 o 4*S

S

400...

C

'0 4 0 S. 6@ 44

S

81 CH- 3

F

-CH-CH--

CH

3

F

bpotmb: 200C

-CH

3 -Gil 3 -CH-CHiQO§Q.

CH

3

C

4 H.-tert.

CH-CH-- O

CH

3 bpo 210C bpo~lmb: 200C The- IH NMR spectra were recorded in deuterochloroformf (CDCI,) or hexadeuterodimethyl suiphoxide (DMSO-d 6 using tetramethylsilafle as internal standard.

Stated is the chemical shift as 8 value in ppmn for the radical R 2 -43- Use-Examples: Example A Pyricularia test (rice) protective t 10 Solvent: 12.5 parts by weight of acetone Emulsifier: 0.3 parts by weight of alkylaryl polyglycol ether To' produce a suitable preparation of active compound, 1 part by weight of active compound is mixed with the stated amount of solvent and the concentrate is diluted with water and the stated amount of emulsifier to the desired concentration.

S S To test for protective activity, young rice plants are sprayed with the active compound preparation to run off point. 5 days after the treatment, the plants are inoculated with an aqueous spore suspension of Pyricularia oryzae. The plants are subsequently placed 0 in a greenhouse at 100% relative atmospheric humidity and S 20

S

The extent of the disease is evaluated 4 days after the inoculation. 0% means an efficacy which corresponds to that of the control, while an efficacy of 100% means that no infection is observed.

In this test, the compounds listed in Examples 8, 16, 18, 20-24, 28, 29, 31, 33 and 34 exhibit, at an active compound concentration of 0.025% by weight in the spray liquor, an efficacy of at least -44 jable A Pyricularia test (rice) protective Active compound Active compound concentration in the spray liquor in Efficacy in Accordins! to the invention: 0, 025

S

9 9 9 9 .999..

9 9 9 *0 *99~ *4 9 0 9.*999 *9 9 *9 a N CH 3 (8) N cH 0,025 (16) 0 0

CH

N 3 (17) 0,025 Table A (continued-I py ricularia test (rice) protective Active compound Active compound concentration in the spray liquor in Efficacy in 0,025

'CH

3 z~: *e4.e* 4 44 40 4 4 444* 4 *444 4* 4* 4.

*4e* .4 44 *44@ 444499 4 .4 *4 4 4.

S

4* (18) 0,025 0,025

CH

3 (21)

CF

3 0,025 0U -46 Table A (fconfinued) Pyricularia-Test (rice) protective Active compound Active compound concentration in the spray liquor in Efficacy in s~: 99. 9 4' 9* 9 4' 9 9.99* 4 9 *949 9*9999 9 4' 99*4 9* 9* 9994' 9 d 9 999999 9 4'.

99 4' 9, 9 0* 9* 9

CH

3

CF

3

-F

0,025 (23) 0 0 N CH 3 0,025 F F (24) 0- 0 C; oC(CH) N C 3 0,025 (28) 0,025 (29) -47 Table A (contiuued) Pyricularia-Test (rice) protective Active compound Active compound concentration in the spray liquor in Efficacy in 4* 4q 9 4 9 4 9 *999*q 9 9* *4 .4 9 4 9 9 9 4 *499 9 9*4* 9.

9* @9 *999 44 4* 9 9999 99*999 4 4q *4 4 S@bt 9* *9 9 0

CF

3 0,025

CH

3 (31)

C(CH

3 3 0,025.

CH

3 20 (33) 0,025

CH

3 (34) -48- Example B Pyricularia test (ice) systemic Solvent: 12.5 parts by weight of acetone 0.3 parts by weight of alkylaryl polyglycol ether To produce a suitable preparation of active compound, 1 part by weight of active compound is mixed with the stated amount of solvent and the concentrate is diluted with water and the stated amount of emulsifier to the desired concentration.

To test for systemic properties, 40 ml of the active compound preparation are poured onto standard soil in which young rice plants were grown. 7 days after the treatment, t the plants are inoculated with an aqueous spore suspension of Pyricularia oryzae. The plants then remain in a greenhouse at a temperature of 25°C and a relative atmospheric humidity of 100% up to the evaluation.

The extent of the disease is evaluated 4 days after the inoculation. An efficacy of 0% means that the infection corresponds to that of the control and an efficacy of 100% means that no infection is observed.

20 In this test, the compounds listed in Examples 8, 16, 17, 21-24, 28, 29, 31 and 34 exhibit, at a concentration of 100 mg of active compound per 100 cm 2 an efficacy of more than S 49 Table B Pyricularia test (rice) systemic Active compounds Application rate in Efficacy mg of active compound in per 100 cm 2 According to the invention: 90 a 0 0 0*0 *0 00* 00 00 9 0 0 0900 0 a 0000 00.00* 0 0 a no.

00 00 00 000* 0 4 0.00 00009 0 0 9.

0 0 0a 0- 0

S-

N N C3 100

CH

3 (16) 100

CH

3 (17) 50 Table B (continued) Pyricular ia test (rice) systemic Active compounds Application rate in Efficacy mg of active compound in per 100 cm' Sq U

S

5 5.55e*

S

S. cc 5

S

*5eS

S

.5.

S

5~5

U

U 5* *55* 5e S S

S..

S

*5 100 'CH 3 (21) 100 F F (22) C1 0 -o0- CF 3

CH

3 100.

(23) -51 Table B (continued) Pyricularia test (rice) systemic Active compounds Application rate in Efficacy mg of active compound in per 100 cm 2 .9 9 9 9 9 a 9999*9 9 9 9C 99 9. 9 9 9 *99* a 9 i 9 9*0e 99 9.

09 a 0 9099 9 a 9990 9 a 9 9 a.

(24) 0 C(CH 3 3

CH

3 (28)

CH

3 N

CH-

(29) 52 Table B (continued) Pyricularia test (rice) systemic Active compounds Application rate in mg of active compound per 100 cm 2 Efficacy in 9 .4 9 9 4 9 9.

99 9 9 99.9 a 9*9#9a

S

9*99 *9 9~ .9 a*.

9 9.

a.

.9 a 9 ~t999 a *999 9* 9 a *9 9

CF

3 15

CH

3 (31)

CH

3 (34) -53- Example C Unciula test (grapevine) protective Solvent: 47 parts by weight of acetone Emulsifier: 3 parts by weight of alkylaryl polyglycol ether To produce a suitable preparation of active compound, 1 part by weight of active compound is mixed with the stated amounts of solvent and emulsifier, and the concentrate is diluted with water to the desired concentration.

p 15 To test for protective activity, young plants are sprayed with the active conpound 1 5 preparation to run off point. After the spray coating has dried on, the plants are dusted with conidia of the fungus Uncinula necator. The plants are subsequently placed in a greenhouse at 23 to 24"C and at a relative atmospheric humidity of about Evaluation is carried out 14 days after the inoculation. An efficacy of 0% means that 20 the infection corresponds to that of the control, and an efficacy of 100% means that no infection is observed.

In this test, the active compound listed in Example 10 exhibits, at an active compound concentration of 25 ppm in the spray liquor, an efficacy of more than 54- Uncinula test (grapevine) protective Active compound 9* 9 9 S 9

S

S..

S

S S

S.

S..

5* S S *5S

S

S S. S aS Efficacy in at an active compound concentration of 25 ppm in the spray liquor Accordinig to the invention:

CH

3 Example D Test with flies (Musca domestica) Test animals: Musca domestica, Reichswald strain (OP, SP, carbamate-resistant) Solvent: 35 parts by weight of ethylene glycol monomethyl ether Emulsifier: 35 parts by weight of nonylphenol polyglycol ether To produce a suitable formulation, three parts by weight of active compound are mixed with seven parts of the abovementioned solvent-emulsifier mixture, and the resulting emulsion concentrate is diluted with water to the respective desired concentration.

15 2 ml of this active compound preparation are pipetted onto filter paper dishes (0 9.5 cm) situated in Petri dishes of corresponding size. After the filter discs have dried, 25 test animals are transferred into the Petri dishes and covered.

The activity of the active compound preparation is determined after 24 hours. 100% means that all the flies have been killed; 0% means that none of the flies have been killed.

In this test, the active compounds listed in Examples 23, 26 and 31 exhibit, at a concentration of 1000 ppm in the active compound preparation, an efficacy of 100%.

-56- Table Test with flies (Musca domestica) Active compound Active compound concentration in the preparation in ppm, Efficacy in According to the invention: a a a. a a 0* C 9*

C

a.

*0Ca a a.

a a a a a a 1000 100

CF

3

CH

3 (23) 1000 100 F F CH 3 (24) Br 0~r 06 1000 100 CH 3 -57- Examnple E Blowfly larvae test/ Development-inhibitory action animals: Lucilia cuprina larvae Solvent: 35 parts by weight of ethylene glycol monomethyl ether Emulsifier: 35 parts by weight of nonylphenol polyglycol ether To produce a suitable preparation of active compound, three parts by weight of active compound are mixed with seven parts by weight of the abovementioned mixture, and the resulting emulsion concentrate is diluted with water to the respective desired concentration.

15 About 20 Lucilia cuprina res. larvae are introduced into a test-tube which contains about I cm 3 of horse meat and 0.5 ml of the active compound preparation. After 48 hours, the activity of the active compound preparation is determined. The test-tubes are transferred in a beaker having a bottom covered with sand. After a further 2 days, the test-tubes are removed and the pupae are counted.

The activity of the active compound preparation is determined by the number of the flies that have hatched after 1.5 times the development time of an untreated control.

100% means that none of the flies have hatched; 0% means that all the flies have hatched normally.

In this test, the active compound listed in Example 31 exhibits, at a concentration of 1000 ppm in the active compound preparation, an efficacy of 100%.

58 TableE Blowfy larvae test development inhibitory action Active compound Active compound concentration in the Efficacy in preparation iii ppm ccording to the invention: *4 4*

S

S.

p. p p p

S

p S P p p S p p *5Pp p p *Spp..

p p p p p. p p.

4* p 1000 100

CH

3 (31) 3

J

Claims

1. Method for protecting plants against attack by unwanted micro-organisms and for controlling animal pests, characterized in that 1,2,3-thiadiazolecarboxylic (thio)esters of the formula 0 9 9 0 990 S *0* S 00 @0 S S 5 o 9 0 9*

9. 00* o* 0@* o904 o 0 *0**0 o 0S go• o 9 0500 0 9. S in which the radicals R 2 and Q have the meanings set forth below CH, ~Q-C CH 3 CH6~ -CH, -CH 3 CH, 60 -CH- 3 -CH 3 -CH 3 a @6 *s S S S S a 6**qOO S *S SO 5 0 S OGSS 6 SeeS S .55555 S 0000 S S C S 55 5555 S S 5* 00 0005 S

555. S 5.555. S .5 5 5505 55 S S S OS S -CH 3 1 H 3 c CH 3 H 3 C N OCF 3 -CH 3 -CH 3 -CH 3 S lc C H 0 N I 0 -61- 5-CH3 0 CH 3 C CH CH 3 4-H 0 CH 3 0 Iu IN -c 2 HA 0 -C 3 0 c 15-CH 3 0 c N cI -CH 3 0 62 -GB 3 0 1 a a. a a a a a a. a a a a. a -GB 3 -GB 3 C, a CF 3 F F F CF 3 F OCF 3 -CH 3 -GB 3 -CH 3 NO0 2 ST~ ROV 63 RlQ R 2 3 0 C C H 3 0 C H 00-c 3 0 CH 3 CH 3 -CH- 3 0 H 3 C a.-CH 3 OCF 3 o -CH 3 0 Br OCF 3 c H00 -C 2 H 5 0 HClC H 04CH 3 64 RlQ R 2 -CH 3 0 N CF 3 0 0 CH 3 -C 3 H7 0/ CH 3 H 7 0 I CH 3 3 H 7 0 CH 1 CH 3 -CH 3 0 65 -CH 3 0 -CH 3 a 0* 9 -CH 3 H C CH3 CH 3 H 3 C CH H 3 C CH 3 C 2 HS 0yCH 2 F CH 2 F 0, CF 3 -CH 3 -CH 3 -CH 3 -CH 3 -o ~7 66 -CH 3 0 0 2 H -CH 3 0 COOCH i-C 3 0 67 -CIH 3 CH 3 CH 3 -CH 3 C. p C C p C. C C C C C CCC... C C Cs. A C A C C C. C C S.C. 9 CCC* C C C C C CCC. eC p C C CC C -CH 3 -CH 3 -CH 3 'C CHO CH, N N -CH 3 -CH 3 b- 3~ CH 3 68 RIQ -CH 3 0 -GCl 3 0 CH(CH 3 2 4 4 4 V V 4 V a. 'V 4- 4V*A S 4 4 9 4* 9 4 *@AV .4 a V V -CH 3 0 I -CH3 0 cI 0 CI S-CH 3 0 GH 3 CH 3 0 N C(CH 3 3 -CH 3 0 0 C H 3 69 -GCl 3 CF:) -GCl 3 0 000*e0 00 0 0 0 0000 0 0 000 000000 0 00 0* 0000 0* 0* *000 0 0 00000 0 00 0 0 6 *0*0 00 0 0* 00 0 CH 3 -CH 3 -CH 3 -GCl 3 CH 3 CH 3 N-CH 3 CF 3 CH 3 -CH 3 0 -CH 3 0 70 R' Q 3 0 CH 3 06 OH 3 CH 3 :-CH 3 O-CH NI. CI 15.0 -CH' 3 0F -CH -CHiFO/" 20 C 3 F A tet -C H 0 0- -O OO .M 250 ar aple to B 0h ir-raim rt h nmlpssado oterhbtt -71- 2. 1, 2, 3 thiadiazolecarboxylic (thio)esters of the formula R' N N- z -R B, B BBS 2: B in which the radicals R' R 2 and Q have the meaninys set forth below CH3 C3 -CH 3 CH CH 3 CH 3 -CH 3 72 Q F -CH 3 0- -CH 3 0 ci F -CH 3 0 "o0 CH 3 -CH 3 0H 3 C -CCH 3 a k H -CH 3 0 -CH 3 0 CH3 HC -CM 3 0 73 (CH3 e b 4e S a a a a a a. a a. a -CH3 -CH 3 -CH 3 -CH 3 a- C -CH 3 74 -CH 3 I a a a a. *a a a a a.. a.. a S a a a a a a a a a S. a a. a a. a. -CH 3 -CH 3 I- Cl CF 3 F F F* CF 3 OCF 3 -CH 3 -CH. 3 -GH 3 NO 2 ~HO c HO OH o SH zo o o H3- CHO3- a a a 4 @.a a a a. a a a a a a a a *aa. a a a a. p. 01 *aa a a a. a 'Ho lcl' CHO- Zo cl 4 9L 76 RlQ B? -CH 3 0 N CF 3 -C 3 H 7 0/ CH 3 CHa CH 3 -C 3 H7 0 s-C 3 0 N C I CH 3 a-C3H7 0 CH3 0CH -CH 3 0 R 1 Q R -OH 3 0 H 3 C CH-. H C -OH 3 0 22K -CH 0 ,S yC 9 aF 25-C3 0 .CF -OH 3 0HCCH CJH 78 Q RQ 3 0 CIH 0 NC a.. *ova COC 3 -C 3 a *0.0 *a 5-CH 3 00 F a :-CH 3 0 CH 3 0 CH 3 0 NH 79 RlQ R? -CH 3 0 I CH 3 CH 3 -CH 3 0 F 0 a o 3 0 555a-CH 3 0 3: 0: RlQ -CH 3 -GCl 3 -CH 3 *.CH 3 CH(CH 3 2 C(CH 3 2 c I 0 0 0**0 *0 C S C. -CH 3 ,-CH 3 -CH 3 CH 3 0~N- CI CH 3 81 Rl ~Q -CH 3 0 CF 3 -CH 3 0 CF 3 CH 3 CH 3 0 CF 3 HH -CH3 0CHF CH3 0 H S.N-CH 3 0,c2H 0 82 Q a -CH 3 0 CH 3 CHH3 3 10-CR 3 0 F -C0- 0H IC 15-CR 3 0F 99. CH-CH--oOF 1 941 -83- 3. Process for preparing 1, 2 3 -thiadiazolecarboxylic (thio)esters of the formula (I) according to Claim 2 characterized in that 1, 2 ,3-thiadiazolecarboxylic acid derivatives of the formula R 1 N (I) S 0 in which 10 R' is as defined in claim 2 and X represents halogen are reacted with (thio)alcohols of the formula oo; H-Q-R 2 15 in which Q and R 2 are each as defined in claim 2. S if appropriate in the presence of an acid binder and if appropriate in the presence of a diluent. 4. Compositions for protecting plants against attack by unwanted micro-organisms and 20 for controlling animal pests, characterized in that it comprises at least one 1, 2, 4- thiadiazolecarboxylic (thio)ester of the formula according to Claim 2. Process for preparing compositions for protecting plants against attack by unwanted micro-organisms and for controlling animals pests, characterized in that 1,2,3- thiadiazolecarboxylic (thio)esters of the formula according to Claim 2 are mixed with extenders and/or surfactants. Dated this 26th day of August 1999 BAYER AKTIENGESELLSCHAFT By Its Patent Attorneys 1 <DAVIES COLLISON CAVE cDO\C^